CN1329107A - Method for reducing dehydrated contraction of water base composite - Google Patents

Method for reducing dehydrated contraction of water base composite Download PDF

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Publication number
CN1329107A
CN1329107A CN01121647A CN01121647A CN1329107A CN 1329107 A CN1329107 A CN 1329107A CN 01121647 A CN01121647 A CN 01121647A CN 01121647 A CN01121647 A CN 01121647A CN 1329107 A CN1329107 A CN 1329107A
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China
Prior art keywords
hydrophobic
hydrophobic materials
list
gram
materialss
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Granted
Application number
CN01121647A
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Chinese (zh)
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CN1207343C (en
Inventor
J·M·哈里斯
J·W·尼利
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Rohm and Haas Co
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Rohm and Haas Co
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Publication of CN1329107A publication Critical patent/CN1329107A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/26—Crosslinking, e.g. vulcanising, of macromolecules of latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C08J2321/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A method for reducing or eliminating syneresis in an aqueous latex composition caused by the flocculation of the latex particles as a result of interaction with hydrophobically modified ethylene oxide based urethane rheology modifiers. The method of the invention involves adding to the aqueous latex composition a molecule containing a single hydrophobic moiety which has a poly-ethylene oxide backbone chain-length of greater than about 5000 Mn. The method of the present invention also increases the viscosity efficiency of the aqueous latex composition by combining a multiphobe with a monophobe.

Description

Reduce the method for aqueous composition synersis
The present invention relates to reduce some aqueous composition synersis and improve the method that this aqueous based systems viscosity is renderd a service simultaneously.Method of the present invention is specially adapted to contain the aqueous composition of latex polymer and thickening material.
Since aqueous composition comes out first, sought always and can improve viscosity and can make this viscosity under various processing conditionss and final use occasion, keep the additive of desired level.Usually this class additive is called " thickening material ".In emulsion paint, adopt thickening material to improve and to control viscosity and to play protective colloid and improve colo(u)rant dispersion, levelling and flowability.In addition, this additive often makes each latex ingredient emulsification, dispersion and stable.In emulsion paint and fabric treatment composition, thickening material often can improve " adhesion " or the cohesiveness of whole composition.Often in cosmetic industry adopt that thickening material is softening to improve as thixotropic agent, the performance of starching and operation.As the additive of paper coating compositions, thickening material can improve the thickening power under the shear conditions.Oil well drilling fluid and oil driving liquid, fire foam and extinguishing fluid, washing composition, leather with paste and finishing agent, binding agent, medicine, Agrotechnical formulation and all various emulsions in, thickening material is used for aforesaid and other aspect of performance equally.
Many well-known thickening materials are for example alginate, casein, kuteera gum, Viscogum BE and Tragacanths of natural product, and the natural product of modification for example comprises the cellulose family of methylcellulose gum, Natvosol and hydroxypropylcellulose.
Many synthetic thickening agents also are effectively, for example carboxy vinyl ether copolymer, acrylic polymers and maleic anhydride styrol copolymer.The thickening material that one of present most important synthetic thickening agent kind is made up of urethane polymer.More specifically, this base polymer comprises the hydrophobic part that is connected with the polyethylene oxide main chain.By amino-formate bond various polymer chain is linked together.Often this class thickening material is called HEUR properties-correcting agent, the HEUR representative oxyethane carbamate of the hydrophobically modified " ".This class hydrophobic group is positioned at the two ends of this polymer chain and comprises at least 20 carbon atoms altogether.Because every end of this polymkeric substance comprises a hydrophobic group, so claim this class properties-correcting agent to be " two hydrophobic materials ".This main polymer chain is made up of the hydrophilic polyether segment.United States Patent (USP) 4,079 has been done detailed narration to this class HEUR properties-correcting agent in 028 and 4,426,485.
The HEUR thickening material can be called " associative thickeners ", this is to form hydrophobic association because the mechanism of their thickenings relates between the hydrophobic part of this thickening material molecule and other hydrophobic surface that comprises other thickening material molecule, pigment or present latex particulate.This and interaction present latex particulate is an emphasis of the present invention.
Some preparation that contains HEUR properties-correcting agent may cause the bridging between the present latex particulate, thereby causes flocculation or " synersis " of this water-based latex system.Synersis is isolated liquid exactly and is taken place and oozes out or " extruding " thinner from separate mutually from gel.Obviously, thisly be separated in that to occur in the water-based emulsion lacquer formulations be unacceptable.Yet, attempt head it off by cancellation or minimizing HEUR properties-correcting agent consumption and can cause said preparation viscosity to be reduced to unacceptable degree.Particularly, cause unacceptable middle reduction of shearing (Krebs-Stormer) viscosity, this value is pressed the reduction of KU or " Krebs Units " and is measured.
The invention solves the synersis problem of water-based emulsion preparation.Unexpectedly, method of the present invention also causes KU efficient to improve.Be to reach measuring of the required amounts of thickener of target viscosities with the KU definitions of efficiency in this article.It is big more promptly to reach the required amounts of thickener of particular viscosity, and then KU efficient is low more.Reaching higher KU efficient reduces simultaneously or eliminates synersis and often relate to and use two kinds of diametrically opposite solutions of processing parameter.Based on prior art, it is wondrous and non-obvious only by a kind of method these two purposes all being reached.
The present invention relates to by adding in the aqueous composition that contains based on the thickening material of carbamate or " HEUR " thickening material, with the synersis that reduces this aqueous composition and improve the method that its viscosity is renderd a service with high-molecular weight list hydrophobic materials (monophobe) or with many hydrophobic materialss blended list hydrophobic materials.This list hydrophobic materials comprises at least one hydrophilic segment and only comprises a hydrophobic segment.The carbon content of this hydrophobic segment it is desirable to greater than 12, be preferably 12-18.Single hydrophobic materials of the present invention can be non-ionic type, anionic, cationic or amphoteric.The Mn of the hydrophilic segment of this list hydrophobic materials (number-average molecular weight) is at least 2,000 and be preferably more than 5,000, be at most 10,000.
This list hydrophobic materials can be chosen the many hydrophobic materialss molecule that comprises various different chain length or molecular weight wantonly.Many hydrophobic materialss are the molecules that contain at least one hydrophilic segment and at least two hydrophobic segments.The many hydrophobic materialss of this class are preferably two hydrophobic materialss (2 hydrophobic segments).The Mn of this pair hydrophobic materials hydrophilic segment is littler than the twice of the Mn of this list hydrophobic materials.The hydrophobicity of the hydrophobic segment of this pair hydrophobic materials is enough to form non-special hydrophobic association.Each hydrophobic segment of preferred this pair hydrophobic materials comprises hydrocarbon part or its suitable thing with at least 8 carbon atoms.
To improve the dual purpose that synersis was renderd a service and reduced to viscosity in order reaching, to have been found that and many hydrophobic materialss and single hydrophobic materials can be combined.Single hydrophobic materials add hydrophobic materials gross weight 66% can be many hydrophobic materialss at the most.Surpass this amount if add many hydrophobic materialss, synersis takes place probably though can improve KU efficient.
Adding the single hydrophobic materials of the present invention in the aqueous composition or the amount of single hydrophobic materials-many hydrophobic materialss mixture to is the function that is contained in the HEUR amounts of thickener in the said composition.The amount of adding mixture of the present invention is at least 1% of this HEUR thickening material weight.Preferred this measured to 2-50% and most preferably is 10-30%.
Embodiment
Various paint formulations have been prepared to check beneficial effect provided by the present invention.Having prepared a kind of standard, not have colo(u)r-in-oil as follows.
Material quantity (%, by volume)
Tamol?681??????????????????????????????4.13
Nuosept?95(Creanova，Inc.)?????????????0.22
Foamaster?AP(Henkel?Corp.)?????????????0.55
Propylene glycol 4.34
Ammoniacal liquor 0.14
Texanol(Texaco?Corp.)??????????????????5.54
Triton?GR-7M???????????????????????????0.25
Rhoplex?HG-74P(Rohm?and?Haas)??????????82.67
Water 2.17
100％
The HEUR rheology modifier that the rom Haars Co., Ltd of PA has bought, RM2020NPR have also been adopted from Philadelphia.
The preparation of two hydrophobic materialss:
Hydrophilic segment=pE0 (average Mn=～8,600)
Hydrophobic segment=C18 part
In 450 gram toluene and 258 grams (0.03 mole) poly-(ethylene glycol) (average Mn is～8, the 600) flask of packing into, stir and be heated to constant boiling point then and residual water-content is removed by Dean Rodney Stark couch water trap.The still temperature is reduced to 90 ℃, adds 17.73 gram (0.06 mole) isocyanic acid stearyl, then add 0.2 gram dibutyl tin dilaurate catalyst again.Stirring is after 1 hour down at 90 ℃, and reaction finishes.
Prepare single hydrophobic materials:
Hydrophilic segment=pEO (average Mn=～10,000)
In 300 gram toluene and poly-(ethylene glycol) monomethyl ether of 300 grams (0.03 mole) (average Mn=～10,000) flask of packing into, stir and be heated to constant boiling point then and residual water-content is removed by Dean Rodney Stark couch water trap.The still temperature is reduced to 90 ℃, adds 8.02 gram (0.03 mole) isocyanic acid cetyl esters, then add 0.2 gram dibutyl tin dilaurate catalyst again.Stirring is after 1 hour down at 90 ℃, and reaction finishes.
The aqueous solution of 20% single hydrophobic materials and/or two hydrophobic materialss is added in the no colo(u)r-in-oil of 150 grams, and gained the results are shown in table 1.
Table 1
Test number ?RM2020 Single hydrophobic materials Two hydrophobic materialss ????KU Suppress synersis?
Standard 5 grams 0 gram 0 gram ????93 Not
Contrast 6.5 gram 0 gram 0 gram ????100 Not
????1 5 grams 1.5 gram 0 gram ????102 Be
????2 5 grams 0 gram 1.5 gram ????＞144 Not *
????3 5 grams 1.2 gram 0.3 gram ????114 Be
????4 5 grams 1.0 gram 0.5 gram ????120 Be
????5 5 grams 0.75 gram 0.75 gram ????135 Be
????6 5 grams 0.5 gram 1.0 gram ????＞144 Be
????7 5 grams 0.3 gram 1.2 gram ????＞144 Not
Comparative Examples 5 grams 1.5 gram @ 0 gram ????82 Not
* synersis is poorer than what expect
@ commercial surfactant Triton X-405 (octyl phenol hydrophobic materials and @1800Mw polyethylene oxide polymer main chain)
In Comparative Examples, use common tensio-active agent to reflect the dysgenic practical situation of this class material elimination synersis of outstanding confessed employing.Apparent from The above results, use this tensio-active agent, its consumption is identical with single hydrophobic materials of the present invention, but reduces the effectiveness (low KU) of thickening material significantly and can not suppress synersis.Yet, because single hydrophobic materials of the present invention and TritonX-405 all are considered to the tensio-active agent of non-ionic type, in view of commercially available tensio-active agent does not have effect, and single hydrophobic materials of the present invention can increase the effectiveness of thickening material and suppress synersis, and this is astonishing.

Claims (10)

1. one kind is reduced synersis and the method that improves the aqueous composition medium viscosity effectiveness that contains thickening material, this method comprises adds high-molecular weight list hydrophobic materials in the described composition to, and this list hydrophobic materials comprises at least one hydrophilic segment and a hydrophobic segment is only arranged.
2. the process of claim 1 wherein this thickening material be based on hydrophobically modified the carbamate rheology properties-correcting agent of oxyethane.
3. the process of claim 1 wherein that the number-average molecular weight (Mn) of this list hydrophobic materials hydrophilic segment is at least 2,000.
4. the method for claim 3, Mn that wherein should list hydrophobic materials hydrophilic segment is 5,000-10,000.
5. the method for claim 1 also comprises many hydrophobic materialss.
6. the method for claim 5, wherein these many hydrophobic materialss are two hydrophobic materialss.
7. the method for claim 6, wherein should the list hydrophobic materials and two hydrophobic materials weight 66% comprise this pair hydrophobic materials at the most.
8. the method for claim 7, wherein the Mw of this pair hydrophobic materials hydrophilic segment is littler than the twice of the Mn of this list hydrophobic materials hydrophilic segment.
9. it is definite to the process of claim 1 wherein that this viscosity is renderd a service the increase of passing through KU unit.
10. the process of claim 1 wherein that said composition contains latex polymer.
CNB011216476A 2000-06-20 2001-06-20 Method for reducing dehydrated contraction of water base composite Expired - Lifetime CN1207343C (en)

Applications Claiming Priority (2)

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US21256100P 2000-06-20 2000-06-20
US60/212,561 2000-06-20

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CN1207343C CN1207343C (en) 2005-06-22

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US (1) US6602948B2 (en)
EP (1) EP1167465B1 (en)
JP (1) JP5069390B2 (en)
KR (1) KR100860127B1 (en)
CN (1) CN1207343C (en)
AU (1) AU782497B2 (en)
BR (1) BR0102442B1 (en)
CA (1) CA2348591C (en)
DE (1) DE60109681T2 (en)
TW (1) TW593529B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2367812A1 (en) * 2002-01-15 2003-07-15 Robert F. Smith Abrasive article with hydrophilic/lipophilic coating
US7402627B2 (en) * 2003-08-18 2008-07-22 Columbia Insurance Company Precursor colorant composition for latex paint
US8329807B2 (en) * 2003-08-18 2012-12-11 Columbia Insurance Company Latex paint film resistant to adverse effects of water, and compositions and methods for making same
US9139676B2 (en) 2003-08-18 2015-09-22 Benjamin Moore & Co. Environmentally friendly colorant compositions and latex paints/coatings
EP1541643B1 (en) * 2003-12-10 2013-03-13 Rohm And Haas Company Nonionic associative thickener containing condensation polymer backbone
FR2873127B1 (en) 2004-07-13 2008-08-29 Omya Development Ag PROCESS FOR THE PRODUCTION OF SELF-ADHESIVE, DRIED OR AQUEOUS SUSPENSION OR DISPERSION PIGMENT PARTICLES CONTAINING INORGANIC MATERIALS AND BINDERS
CN102786655B (en) * 2012-08-30 2014-04-02 武汉科技大学 Branched waterborne polyurethane with hydrophobic group and preparation method thereof
CN102898612B (en) * 2012-10-31 2014-06-25 丽水学院 Preparation method of linear water-based polyurethane thickener containing hydrophobic side bases
EP3305863A1 (en) * 2016-10-07 2018-04-11 Basf Se Method for the preparation of flocculation stable polyisocyanates of (cyclo)aliphatic diisocyanates in solvents

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US3770684A (en) 1970-06-25 1973-11-06 Troy Chemical Corp Latex compositions containing bodying agents
US3998973A (en) 1975-04-07 1976-12-21 R. T. Vanderbilt Company, Inc. Thickening composition
US4079028A (en) 1975-10-03 1978-03-14 Rohm And Haas Company Polyurethane thickeners in latex compositions
US4096327A (en) 1977-01-05 1978-06-20 Fmc Corporation Modified kappa-carrageenan
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US4327008A (en) 1980-12-29 1982-04-27 Ppg Industries, Inc. Urethane rheology modifiers and coating compositions containing same
US4426485A (en) 1982-06-14 1984-01-17 Union Carbide Corporation Polymers with hydrophobe bunches
US4499233A (en) 1983-05-03 1985-02-12 Nl Industries, Inc. Water dispersible, modified polyurethane and a thickened aqueous composition containing it
SE501624C2 (en) 1992-09-15 1995-04-03 Berol Nobel Ab Polyurethane, its use and water-borne paint containing the polyurethane as a thickener
US5281654A (en) 1993-01-14 1994-01-25 Rohm And Haas Company Polyurethane mixture
US5973053A (en) 1995-06-05 1999-10-26 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite clay material and method for producing the same, blend material and composite clay rubber using the same and production method thereof
US6011106A (en) 1997-09-29 2000-01-04 Rohm And Haas Company High-build low-sag aqueous coating composition
EP0997502A1 (en) * 1998-10-30 2000-05-03 Hercules Incorporated Combinations of associative thickeners and aqueous protective coating compositions
US6337366B1 (en) * 1999-03-25 2002-01-08 Rohm And Haas Method of improving viscosity stability of aqueous compositions

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JP2002020614A (en) 2002-01-23
BR0102442A (en) 2002-02-19
AU782497B2 (en) 2005-08-04
BR0102442B1 (en) 2011-10-04
JP5069390B2 (en) 2012-11-07
EP1167465B1 (en) 2005-03-30
DE60109681D1 (en) 2005-05-04
CA2348591C (en) 2005-02-08
AU5179401A (en) 2002-01-03
US6602948B2 (en) 2003-08-05
KR100860127B1 (en) 2008-09-25
CN1207343C (en) 2005-06-22
DE60109681T2 (en) 2006-03-09
CA2348591A1 (en) 2001-12-20
KR20010114142A (en) 2001-12-29
EP1167465A1 (en) 2002-01-02
US20020010255A1 (en) 2002-01-24
TW593529B (en) 2004-06-21

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Granted publication date: 20050622